JP6929780B2 - New heat-processable fluoropolymer - Google Patents

Description

Cross-reference to related applications This application claims priority from European Patent Application Publication No. 15154654.6 filed on February 11, 2015, and all content of this application is for all purposes. To be incorporated herein by reference.

The present application relates to novel heat-processable fluoropolymers containing ethylene and chlorotrifluoroethylene and / or tetrafluoroethylene, as well as multilayer articles containing them.

Fluoropolymers are widely used to protect the surface from corrosion by weathering agents and chemicals.

Industrial equipment made of metal can be protected by corrosion using a fluoropolymer-based coating. The fluoropolymer-based coating ensures chemical inactivity to the eroded environment. Such coatings may need to be applied directly to various metal surfaces such as stainless steel, galvanized steel, carbon steel, aluminum, copper, bronze, brass, and specialty alloys.

Similarly, polyamides, which exhibit poor chemical resistance and permeability to gasoline containing polar substances, have also been combined with fluoropolymers to form multi-layered articles, for example in the manufacture of fuel pipes in the automotive industry.

Among fluoropolymers, copolymers of ethylene (E) and chlorotrifluoroethylene (CTFE) and / or tetrafluoroethylene (TFE), which may optionally contain other monomers, are in the art. It is known and has been suggested to be useful for coating polyamide or metallic articles.

For example, European Patent Application No. 1241001A states that ethylene (E), chlorotrifluoroethylene (CTFE) and / or tetrafluoroethylene (TFE), and acrylic monomers. Disclosed are articles made in multiple layers, including at least a layer containing a heat-processable copolymer as a main component and one layer containing a polyamide as a main component. In the examples, a copolymer of ethylene / chlorotrifluoroethylene (ECTFE) further containing a monomer derived from n-butyl acrylate (n-BuA) is disclosed. However, this patent does not provide any examples of ECTFE copolymers containing repeating units derived from acrylic acid, nor does it describe the coating of metal substrates.

In the International Publication No. 2013/174915 pamphlet (SOLVAY SPECIALTY POLYMERS ITALY SPA), it is a composition for use as a primer coating on the surface of galvanized steel, and at least one kind of ethylene among the components. / Compositions comprising chlorotrifluoroethylene (ECTFE) polymers are disclosed. The ECTFE polymer may also contain up to 10 mol% copolymerizable comonomer such as acrylic acid and methacrylic acid. However, the ECTFE polymer disclosed therein contains 50/50 mol% ethylene / chlorotrifluoroethylene. The composition is also applied to the galvanized steel surface as a primer coating and then further coated with a topcoat containing the same ECTFE polymer. This patent application also does not mention anything about the coating of polymer substrates.

ECTFE copolymers that may optionally contain acrylic monomers are described in US Patent Application No. 2001/0027236 (AUSIMONT SPA), US Patent Application No. 2002/015618 (AUSIMONT SP). A.), And US Patent Application No. 2009/0326154 (SOLVAY SOLEXIS SPA). Neither of the patent applications discloses or exemplifies an ECTFE copolymer containing a specific amount of acrylic acid monomer.

International Application No. 2011/102549A Pamphlet (Fuji Film Co., Ltd.) discloses a polymer sheet having properties suitable for use as a back sheet for a solar cell. The polymer sheet includes a support and a polymer layer laminated directly on the support. The polymer is a polymer containing a repeating unit represented by the following general formula (1):
-(CFX _1- CX _{2 X 3} ) -General formula (1)
(In the formula, X ₁ , X ₂ and X ₃ represent any of a hydrogen atom, a fluorine atom, and a perfluoroalkyl group having 1 to 3 carbon atoms, respectively).
Further, the polymer may _{be a polymer produced by copolymerizing a monomer represented by − (CFX 1} − CX _{2 X 3} ) − with a copolymerizable monomer other than the former monomer. In particular, the following are described: Copolymers of chlorotrifluoroethylene, tetrafluoroethylene and acrylic acid (AA / TFE / CTFE), and copolymers of ethylene, chlorotrifluoroethylene and acrylic acid (AA / CTFE). / E).

The amount of the repeating unit represented by the general formula (1) is 70% by mass or more, preferably 80 to 97% by mass. The polymer is preferably a repeating unit having a carboxyl group in an amount of 0.03% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, still more preferably 0.5 to 5% by mass. including. As a result, the mass percentage of ethylene-derived repeating units in the terpolymer is 9.99 to 29.996% by mass, more preferably 2.5 to 10% by mass.
An aqueous polymer dispersion (polymer latex) having a core and a polymer shell having a repeating unit represented by − (CFX ₁ − CX _{2 X 3) − is preferred.}

More specifically, in Example 27 in Table 2A on page 46, a core made from CTFE / E and a shell made from AA / CTFE / E are represented by the general formula (1). A shell having a repeating unit content of 99% is disclosed.

Copolymers of ethylene, chlorotrifluoroethylene, and acrylic acid are disclosed in this application, and the amount of acrylic acid is 0.03 to 20% by mass. The polymer is made with an aqueous dispersion, resulting in a polymer latex with a core and shell. The composition containing the polymer is then obtained by mixing the latex with water in the presence of a surfactant.

Therefore, this document does not disclose the terpolymer made from CTFE or TFE, AA, and E contained in the amounts of CTFE / TFE and E of the present invention. Moreover, this document does not describe at all the issue of adhesion between the polymer layer and the metal layer.

International Publication No. 2010/096027 Pamphlet (WU HUEY-SHEN) discloses fluorochloroionomers suitable for use in polymer electrolyte fuel cells. Example 6 discloses an intermediate that is a terpolymer of E / CTFE / AA that is synthesized as disclosed in Example 4 and further refers to US Pat. No. 6,228963. .. Here, the molar ratio between CTFE and AA in the terpolymer is considered to be 5: 1. The polymer copolymerization reactions described herein can occur in both aqueous and solvent systems. However, emulsion polymerization (including miniemulsions and microemulsions) is preferred.

Therefore, this document does not disclose a terpolymer made from CTFE or TFE, AA, and E, which is included in the molar ratio of CTFE and AA of the present invention. Moreover, this document does not describe at all the issue of adhesion between the polymer layer and the metal layer.

Applicants have made compositions containing polymers that can provide excellent adhesion to multiple substrates, especially with long-term exposure to harsh environmental conditions and without the need for a primer layer. I realized that was still needed.

Applicants have surprisingly found that the above problems can be solved by using a novel copolymer containing a specific amount of acrylic acid-derived repeating units.

Therefore, in the first aspect, the present invention
(A) Repeat units derived from 51 mol% to 65 mol% chlorotrifluoroethylene (CTFE) and / or tetrafluoroethylene (TFE);
(B) 0.5 mol% to 10 mol% repeating units derived from acrylic acid (AA); and (c) the sum of the percentages of repeating units (a), (b), and (c) to 100 mol% 31 mol% to 45 mol% ethylene (E) -derived repeating unit in such an amount;
With respect to the polymer (P), which is essentially a polymer [polymer (P)], the above-mentioned molar percentage is based on the total number of moles of the repeating unit of the polymer (P).

Applicants can surprisingly attach the polymers of the invention to the surfaces of both polymer and metal substrates, resulting in a coating layer with excellent adhesion to said substrates. I found that it was possible.

Also, the applicant was surprisingly good at the polymer of the present invention between the coating layer and the plurality of substrates without the need to sandwich a primer coating between the coating layer and the substrate. It was also found that adhesiveness can be obtained.

Finally, Applicants can favorably process polymers of the invention containing more than 50 mol% CTFE at lower temperatures than polymers containing 50 mol% CTFE, resulting in degradation during processing. I also found that there was no such thing.

Next, in the second aspect, the present invention
-A substrate having at least one surface [Surface (S)] and
-With the layer (L1), which is at least one layer [layer (L1)] directly adhered to the surface (S) and contains the polymer (P) as defined above.
Regarding articles including.

When the substrate is a polymeric substrate, the layer (L1) advantageously provides improved mechanical properties, reduced water vapor permeability, and improved lifetime. When the substrate is a metallic substrate, the layer (L1) advantageously provides excellent protection against corrosion.

For the purposes of this specification and subsequent claims, the use of parentheses in expressions such as "polymer (P)", "surface (S)", "layer (L1)", etc. is the rest of the statement. The purpose is only to make it easier to distinguish the symbols or numbers from, and therefore the parentheses may be omitted.

For the purposes of this specification and subsequent claims, the expressions "mol%", "mol%", "mol%", "mol%" are the total amount of all components in the mixture (expressed in moles). The amount of the mixture component (represented in moles) divided by (is) and multiplied by 100 is shown.

The expression "becomes essential" is intended to indicate that small amounts of chain ends, defects, irregularities, and monomer rearrangements are allowed in the polymer (P).

The polymer (P) is typically measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min according to ASTM D-3418, at least 5 J / g, preferably at least 10 J / g, more preferably. Has a heat of fusion of at least 30 J / g. In a preferred embodiment, the polymer (P) has a heat of fusion of about 18.6 J / g.

The polymer (P) is typically measured at 225 ° C., 2.16 kg according to ASTM D-1238 standard procedure, 0.01-75 g / 10 min, preferably 0.1-50 g / 10 min. More preferably, it has a melt flow index of 0.5 to 30 g / 10 minutes. In a preferred embodiment, the polymer (P) has an MFI of about 3 g / 10 min (225 ° C / 2.16 kg).

The polymer (P) suitable for the method of the present invention typically has a melting point ( _Tm ) of up to 250 ° C., preferably up to 220 ° C. The polymer (P) typically has a melting point of at least 120 ° C, preferably at least 150 ° C. More preferably, the polymer (P) has a melting point ( _Tm ) of 160-200 ° C, more preferably 170-195 ° C. Melting points are measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min according to ASTM D-3418.

Preferably, the repeating unit derived from chlorotrifluoroethylene (CTFE) and / or tetrafluoroethylene (TFE) is 53 mol% to 62 mol%, more preferably 53 mol% to 62 mol% based on the total number of moles of the repeating unit of the polymer (P). The amount is 54 mol% to 60 mol%.

Preferably, the repeating unit derived from acrylic acid (AA) is in an amount of 0.5 mol% to 9 mol%, more preferably 1 mol% to 9 mol% based on the total number of moles of the repeating unit of the polymer (P). Is.

The repeating unit derived from ethylene (E) is, for example, 25 mol% to 48.5 mol%, more preferably 29 mol% to 46.5 mol% based on the total number of moles of the repeating unit of the polymer (P). There may be. Good results were obtained with an amount of 31 mol% to 45 mol% based on the total number of moles of the repeating unit of the polymer (P).

In a preferred embodiment, the polymer (P) is
(A) 58 mol% to 60 mol% repeating units derived from chlorotrifluoroethylene (CTFE);
(B) 1 mol% to 9 mol% repeating unit derived from acrylic acid (AA); and (c) 31 mol% to 41 mol% repeating unit derived from ethylene (E);
The above-mentioned molar percentage is based on the total number of moles of the repeating unit of the polymer (P).

In a more preferred embodiment, the polymer (P) is
(A) 58 mol% to 60 mol% repeating units derived from chlorotrifluoroethylene (CTFE);
(B) 1.2 mol% to 8.5 mol% repeating units derived from acrylic acid (AA); and (c) 31.5 mol% to 40.8 mol% repeating units derived from ethylene (E). unit;
The above-mentioned molar percentage is based on the total number of moles of the repeating unit of the polymer (P).

Polymers (P) containing repeating units derived from ethylene (E) and repeating units derived from chlorotrifluoroethylene (CTFE) are identified herein as ECTFE copolymers; repeating units derived from ethylene (E) and Polymers (P) containing repeating units derived from tetrafluoroethylene (TFE) are identified herein as ETFE polymers below.

In the present invention, the ECTFE polymer is preferable.

The polymer (P) of the present invention is polymerized by reacting ethylene (E) with chlorotrifluoroethylene (CTFE) and / or tetrafluoroethylene (TFE) in the presence of acrylic acid (AA). By doing so), it can be synthesized advantageously.

The reaction (polymerization) is preferably carried out in suspension, in an organic medium, or in an aqueous medium.

Preferably, a dispersant such as methanol can be further added to the suspension.

Preferably, the reaction (polymerization) is at a temperature of −40 ° C. to + 100 ° C., more preferably −20 ° C. to + 50 ° C., still more preferably −15 ° C. to + 30 ° C., and 0.5 to 100 bar, more preferably 5. It is carried out at a pressure in the range of ~ 40 bar.

Preferably, the reaction (polymerization) is carried out in the presence of at least one radical initiator.

Suitable radical initiators are bis-acyl peroxides such as bis-trichloroacetyl-peroxide (TCAP) and bis-dichlorofluoroacetyl-peroxide; dialkyl peroxides such as diterbutyl peroxide; ammonium salts of persulfate or perphosphate or It is selected from the group containing water-soluble inorganic peroxides such as alkali metal salts; dialkylperoxydicarbonates;

Preferably, acrylic acid (AA) is supplied in the form of a solution.

Preferably, ethylene (E) is continuously supplied during polymerization.

Examples of articles of the present invention include ducts, industrial tubes, pipes, pumps, and tanks.

The polymer (P) is advantageously obtained in the form of a dry powder. More preferably, the dry powder has a particle size of 50-250 μm.

Preferably, the substrate is a polymer substrate or a metal substrate.

Typical polymer substrates include, for example, polyamide substrates, such as polyarylamide substrates such as Exef® PArA, and polyimide substrates. For example, suitable polyamide substrates include polyamide 6 (PA6), polyamide 66 (PA66), polyamide 11 (PA11), polyamide 12 (PA12), and polyamide 612 (PA612). Polyamides, for example hexamethylenediamine carbamate and N, protected amine, such as N'- dicinnamylidene-1,6-hexanediamine; for example C ₄ -C ₂₀ aliphatic diamines, such as dodecyl diamine and didecyl diamine; such as para - One or more diamines such as aromatic diamines such as xylylenediamine may be optionally contained.

Typical metal substrates include, for example, stainless steel, zinc-plated steel, carbon steel, copper, aluminum, iron, zinc, cadmium, magnesium, brass, bronze, Monel®, Inconel®. ..

The thickness of the layer (L1) is not particularly limited. Preferably, the thickness of the layer (L1) is 10 to 1500 μm, more preferably 250 to 1200 μm.

Preferably, the layer (L1) is a continuous layer that completely covers the surface (S).

The article of the present invention is advantageous.
(I) A step of preparing a base material having at least one surface (S);
(II) A step of producing the layer (L1) which is at least one layer (L1) directly adhered to the surface (S) and contains the polymer (P) defined above;
Can be obtained by a method including.

When a metal substrate is used, after step (I) and in order to obtain a stronger adhesion between the substrate and the layer (L1), in order to obtain a rough surface (S) and in order to obtain a stronger bond between the substrate and the layer (L1). The step (Ia), which is a pretreatment of the surface (S), is preferably performed before the above. Any suitable surface treatment such as sandblasting, grid blasting, etching, etc. may be used for this purpose.

Further, for the purpose of removing surface contaminants and zinc corrosion products of the zinc-plated base material, the step (Ib), which is preferably cleaning of the surface (S), is the step (I) or the step (I-). It is performed after a) and before step (II). For example, the steps can be performed by ammonia cleaning, alkaline solution cleaning, and solvent cleaning.

For the purpose of obtaining good mechanical adhesion of the surface coating, the profiling step (Ic) is carried out after step (I), step (Ia), or step (Ib) and step (II). ) May be done. For example, in step (Ic), sweep blasting, phosphate treatment, and the use of vinyl butyral acid etching cleaning primers, or acrylic acid mobilization treatment may be used.

In a preferred embodiment, step (II) is performed by a powder coating method such as electrostatic deposition, fluidized bed, electrostatic spraying and the like.

Typically, electrostatic spraying is done by an electrostatic spray gun. It utilizes the principle of electrophoresis in which electrically polarized particles are attracted to a grounded or conversely charged surface.

If electrostatic spraying is used, the power settings can be appropriately selected by one of ordinary skill in the art. Good results were obtained by operating at 10-60 kV and 5 μA-40 μA using an OptiFlex® L spray gun from ITW Gema AG.

Typically, the layer thickness obtained by electrostatic spraying is 10 to 1500 μm, more preferably 250 to 1200 μm.

When electrostatic spraying is used, a composition [composition (C1)] containing at least one polymer (P) as defined above and optionally additional components is preferably used. .. More preferably, when electrostatic spraying is used, the synthetically obtained powdered polymer (P) is first subjected to a grinding step and then a sieving step in order to reduce the particle size of the powder. Is done.

Preferably, the grinding step is carried out using standard milling such as, for example, ball mills, rod mills and the like.

Preferably, the sieving step is performed using a sieve (80 or more US standard mesh) having a mesh size of less than 200 μm.

Suitable additional ingredients may be selected from organic and / or inorganic fillers such as carbon black, mica, and polyphenylene sulfone-based additives (PPSO2) sold under the Trademark Ceramer®. can.

Preferably, the composition (C1) comprises 60-100% by weight of the polymer (P).

Typically, the composition (C1) prepares the polymer (P) disclosed above and optionally mixes the polymer (P) with other components defined above in appropriate amounts. Can be produced by The mixing step is preferably carried out in a suitable powder mixing device such as a vertical mixer or a horizontal mixer.

In another embodiment, step (II) is performed by compression molding.

When compression molding is used, the polymer (P) is first preheated or molded to obtain a plate made from the polymer (P). The plate is then placed on the surface of the metal portion of the article in the press, heated to a suitable temperature and then pressed.

The temperature and pressure can be selected by those skilled in the art depending on the polymer (P) used. Good results were obtained by operating at a temperature of 180 ° C. to 300 ° C. and a hydrostatic pressure of 50 to 100 bar.

Typically, the layer thickness obtained by compression molding is up to 1500 μm, for example 100-1500 μm.

When a polymer substrate is used, the articles of the invention can be by electrostatic spraying disclosed above, by compression molding disclosed above, or at least a composition comprising the polymer (P) [composition (C2)]. Can be obtained by coextrusion with the polymer substrate. One or the other choice of these techniques is based on the intended use for the multilayer article of the present invention, as well as the desired thickness of the layer (L1).

For example, multi-layer articles intended for use as pipes, tubes, films, sheets and plaques are preferably manufactured by coextrusion.

Typically, coextrusion techniques include coextrusion lamination, coextrusion blow molding, and coextrusion molding.

The multilayer article of the present invention is preferably produced by coextrusion of the layer (L1) and a polymer substrate.

If the disclosure of any patent, patent application, and publication incorporated herein by reference conflicts with the description of the present application to the extent that the term may be obscured, this description shall prevail.

The present invention will be described in more detail below with reference to the following examples, but the object of the examples is merely exemplary and does not limit the scope of the invention.

Raw material Chloroform is Sigma-Aldrich Corp. I bought from.

Chlorotrifluoroethylene (CTFE) is available from Honeywell International Inc. I bought from. Ethylene (E) is SIAD S. p. A. I bought from. Acrylic acid (AA) was purchased from Sigma-Aldrich. Hydroxypropyl acrylate (HPA) is available from Sigma-Aldrich Corp. I bought from. Hydroxyethyl acrylate (HEA) is available from Sigma-Aldrich Corp. I bought from. Polyamide PA612 was purchased from Schulman. Polyarylamide IXEF® PARA is a SOLVAY SPECIALTY POLYMERS U.S.A. S. A. Obtained from. The E / CTFE / AA terpolymer having a molar ratio of 45.2 / 50 / 4.8 is SOLVAY SPECIALTY POLYMERS ITALY S.A. p. A. Obtained from.

With synthetic 185.7 ° C. melting point Example 1 - Polymer _(P) (T m), heat of fusion of 18J / g (ΔH2f), and (measured at 225 ℃ / 2.16Kg) 3g / 10 min MFI Polymer (P-1) Ethylene / chlorotrifluoroethylene / acrylic acid (E / CTFE / AA) 36.2 / 59 / 4.8 terpolymer was synthesized as follows.

In an enamel-drawn autoclave with a baffle and agitate at 600 rpm, 3 liters of desalinated water, 102 g of chloroform, 33 ml of a solution of acrylic acid (AA) (20% by volume) and water (80% by volume), and 7 kg. Chlorotrifluoroethylene was introduced.

The temperature was then set to 15 ° C. and ethylene was supplied until the absolute pressure was 8.2 bar.

At the time of polymerization, the radical initiator trichloroacetylperoxide (TCAP) contained in isooctane, which had a titer concentration of 0.12 g TCAP / ml and was maintained at -17 ° C., was continuously supplied to the autoclave in the form of a solution. ..

Also, during polymerization, 33 ml of the same solution of acrylic acid and water was supplied at 20, 40, 60, 80, 100, 120, 140, 160, and 180 g of ethylene consumption.

The polymerization continued for about 540 minutes. The pressure was kept constant by continuously supplying ethylene to the reactor with an ethylene consumption of up to 200 g for the entire time.

At the end of the polymerization, the product obtained from the autoclave was dried at 120 ° C. for about 16 hours.

1414 g of polymer (P-1) was obtained in powder form.

The following E / CTFE / AA terpolymers in dry powder form with molar contents of 39.6 / 59 / 1.4 (Polymer P-2) and 32.7 / 59 / 8.3 (Polymer P-3). Was further synthesized according to the procedure detailed above by adjusting the supply of acrylic acid.
-Polymer (P-2): E / CTFE / AA terpolymer in dry powder form with a molar content of 39.6 / 59 / 1.4 and a _{Tm of 180.8 ° C .;}
-Polymer (P-3): E / CTFE / AA terpolymer in dry powder form with a molar content of 32.7 / 59 / 8.3 and a _{Tm of 181.8 ° C .;}

The polymers P-1, P-2, and P-3 were ground in a ball mill for about 10 minutes and then sifted through an 80US standard mesh sieve.

Example 2-Synthesis of Comparative Polymers Containing Hydroxypropyl Acrylate (HPA) 3 liters of desalinated water, 60 g of chloroform and 20 ml of hydroxypropyl acrylate (HPA) in an enamel-drawn autoclave with a baffle plate and agitated at 600 rpm. A solution of (50% by volume) and water (50% by volume) and 7 kg of chlorotrifluoroethylene were introduced.

20 ml of the same solution of acrylic acid and water was supplied at 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, and 280 g of ethylene consumption to polymerize. This was done according to the procedure disclosed in Example 1 above.

The polymerization continued for about 490 minutes. At the end of the polymerization, the product obtained from the autoclave was dried at 120 ° C. for about 16 hours.

A 1780 g polymer (hereinafter referred to as “HPA-1”) having a molar composition E / CTFE / HPA of 36/59/5 was obtained in powder form. Additional analysis showed that the melting point was 180 ° C and the MFI (measured at 220 ° C / 2.16 kg) was 0.7 g / 10 min.

The powdered E / CTFE / HPA terpolymer having a molar content of 39.9 / 59 / 1.15 (hereinafter referred to as “HPA-2”) was synthesized according to the same procedure with an adjusted HPA supply.

Example 3-Synthesis of Comparative Polymers Containing Hydroxylethylene Acrylate (HEA) 3 liters of desalinated water, 105 g of chloroform and 12 ml of hydroxyethyl acrylate (HEA) in an enamel-drawn autoclave with a baffle plate and agitated at 600 rpm. A solution of (25% by volume) and water (75% by volume) and 7 kg of chlorotrifluoroethylene were introduced.

The same solution of 12 ml of acrylic acid and water was supplied at 20, 40, 60, 80, 100, 120, 140, 160, and 180 g of ethylene consumption and the polymerization was carried out according to the procedure disclosed in Example 1 above. went.

The polymerization continued for about 370 minutes. At the end of the polymerization, the product obtained from the autoclave was dried at 120 ° C. for about 16 hours.

A 1250 g polymer (hereinafter referred to as “HEA-1”) having a molar composition E / CTFE / HEA of 39.7 / 59 / 1.3 was obtained in powder form. Additional analysis showed that the melting point was 176.2 ° C and the MFI (measured at 220 ° C / 2.16 kg) was 8.4 g / 10 min.

These comparative polymers were also ground in a ball mill for about 10 minutes and then sifted through an 80US standard mesh sieve.

Example 4-Manufacture of Multilayer Articles A book comprising a polymer base material or a metal base material and a layer containing the polymers (P-1), (P-2), and (P-3) adhered to the base material. The multilayer article of the invention was produced as disclosed below.

First, plates of polymers (P-1), (P-2), and (P-3) with a thickness of 300 μm were prepared as follows.

40-100 g of each polymer (P-1), (P-2), and (P-3) powder was placed in a frame (130 x 130 x 0.6 mm). Then, two sheets of polytetrafluoroethylene (PTFE) foil were placed one above the other to cover the powder in the frame. The frame was then placed between the two steel plates and then between the press plates. The press plate was then heated at 220-240 ° C. for 5 minutes. Subsequent procedures are as follows: pressure application (16 tonnes / 4.5 inch), degassing for 2 minutes, and second pressure application (16 tonnes / 4.5 inch). Finally, a water cooling step to room temperature was performed.

Plates of comparative polymers (HPA-1), (HPA-2), and (HEA-1) were also made according to the same procedure.

Multilayer article containing 4a-polymer substrate (by compression molding)
A 300 micron thick molded PA612 plaque and a polymer (P-1) plaque obtained as disclosed above were preheated at 240 ° C. for 5 minutes in a frame (size 130 x 130 x 0.6 mm). Overlaid with. The plaque was formed at 240 ° C. for 4 minutes under a pressure of 75 bar. Then, rapid cooling was performed in a cold water plate.

A 300 micron thick IXEF® PArA plaque and a polymer (P-1) plaque obtained as disclosed above were laminated and integrally molded according to the same procedure.

Plaques of PA612 and IXEF® PArA were molded with the comparative polymer (HPA-1) according to the same procedure.

Multi-layer article containing 4b-metal substrate (by compression molding)
A 300 micron thick copper plaque was first washed with acetone and then placed on a 1.5 mm thick polymer (P-2) molded plaque obtained as disclosed above at 225 ° C. for 5 minutes. They were overlapped in a preheated frame (size 130 x 80 x 1.5 mm). The molding step was carried out at 225 ° C. for 4 minutes under a pressure of 80 bar. Then, rapid cooling was performed in a cold water plate.

A 300 micron thick aluminum plaque was treated in the same manner and then overlaid on a 1.5 mm thick polymer (P-2) molded plaque obtained as disclosed above and disclosed above for copper plaques. Processed according to the street.

Plaques of copper and aluminum as well as comparative polymers (HEA-1) and (HPA-2) were also made according to the same procedure.

Multi-layer article containing 4c-galvanized metal substrate (by electrostatic powder coating)
The surface of the galvanized steel test piece (15 × 15 cm) was sandblasted (using 16 mesh sand) and washed with ammonia.

The respective polymers (P-1) and (P-3) were powder coated with an ITW Gema AG OptiFlex® L spray gun operating at 30-50 kV and 15 μA-30 μA. It was applied on top of the washed surface.

The coated specimen was heated in an oven at 220 ° C for 20 minutes and then cooled to 25 ° C.

A uniform coating was obtained on the surface of each test piece with no cracks or visible defects. No discoloration was observed during heating / cooling of the coated specimen.

The second layer of coating, each containing polymer (P-1) or (P-3), was applied according to the same procedure as disclosed above. Similar results were obtained for the appearance.

Example 5-Evaluation of Adhesiveness 5a-Adhesiveness of Multilayer Articles Containing Polymer Substrate The adhesiveness of the multilayer articles obtained in Example 4a disclosed above was obtained at 23 ° C. and 50% R.I. Evaluated by peeling test performed according to ASTM D1876 at H (relative humidity).

The results are reported in Table 1 below.

Since the polymer HPA-1 had already peeled off from the PA612 substrate before the start of the test, no adhesion of HPA-1 to PA612 was performed.

The above results clearly show that the use of the polymer (P-1) of the present invention gives better results in terms of adhesion to various polymer substrates.

Adhesiveness of Multilayer Articles Containing 5b-Metal Substrate The adhesiveness of the multilayer articles obtained in Example 4b disclosed above was obtained at 23 ° C. and 50% R.I. Evaluated by peeling test performed according to ASTM D1876 at H (relative humidity).

The results are reported in Table 2 below.

The above results clearly show that the use of the polymer (P-2) of the present invention gives better results in terms of adhesion to various metal substrates.

Adhesiveness of Multilayer Articles Containing 5c-Zinc Plated Metal Substrate The adhesiveness of the multilayer articles obtained in Example 4c disclosed above was obtained at 23 ° C. and 50% R.I. Evaluated by peeling test performed according to ASTM D1876 at H (relative humidity). This test was performed several hours after the multi-layer article was manufactured (t = 0).

An accelerated aging test was also conducted with the aim of loading the multilayer article by exposing it to steam. After exposing the multilayer article to steam at 85 ° C. for 10 days (t = 10), the adhesiveness was evaluated by a peeling test.

The results are reported in Table 3 below.

The above results clearly show that the polymers of the present invention can provide excellent adhesion to galvanized metal substrates, even after exposure to harsh conditions (humidity).

Applicants attempted to perform the same test using polymer HPA-1 for comparison. However, the applicant has found that it is not possible to obtain a continuous film after electrostatic deposition and heating of HPA-1.

A dynamic time sweep test (according to ASTM D4440) was performed to show the tendency of HPA-1 to crosslink under working conditions. The test was performed with a rheometrics RMS800, a leogoniometer, in a parallel plate configuration (d = 25 mm) at 230 ° C. The frequency was 1 rad / s. Complex viscosity (η-eta) was observed for 1 hour as a function of time. The results are reported in Table 4 below.

Example 6-Evaluation of Deterioration The optical properties of the ECTFE copolymer of the present invention and the ECTFE copolymer containing 50% by weight CTFE were measured using instrument BYK's Spectroguide D45 10 °.

Yellowness (B *, YI and WI) was evaluated according to ASTM E-313.

The results are reported in Table 4 below.

The above results clearly show that E / CTFE / AA terpolymers with a CTFE content of 50 mol% are not stable and are more prone to deterioration.

Claims (9)

(A) 58 mol% to 60 mol% repeating units derived from chlorotrifluoroethylene (CTFE);
(B) 1 mol% to 9 mol% repeating units derived from acrylic acid (AA); and (c) the sum of the percentages of the repeating units (a), (b), and (c) to 100 mol%. 31 mol% to 41 mol% repeating units derived from ethylene (E) in such amounts;
It is a polymer [polymer (P)] that is essentially made from
The above-mentioned molar percentage is based on the total number of moles of the repeating unit of the polymer (P), that is, the polymer (P). (A) 58 mol% to 60 mol% repeating units derived from chlorotrifluoroethylene (CTFE);
(B) 1.2 mol% to 8.5 mol% repeating units derived from acrylic acid (AA); and (c) 31.5 mol% to 40.8 mol% repeating units derived from ethylene (E). unit;
The polymer (P) according to claim 1, wherein the polymer (P) is composed of the above-mentioned molar percentage, which is based on the total number of moles of repeating units of the polymer (P). (A) 5 of 8 mol% to 6 0 mol%, the repeating units derived from chlorotrifluoroethylene (CTFE);
(B) 1 mol% to 9 mol% repeating units derived from acrylic acid (AA); and (c) the sum of the percentages of the repeating units (a), (b), and (c) to 100 mol%. in amounts such that, of 31 mole% to 4 1 mole%, repeating units derived from ethylene (E);
It is a polymer [polymer (P)] that is essentially made from
The above-mentioned molar percentage is based on the total number of moles of the repeating unit of the polymer (P), that is, the polymer (P).
The method for producing ethylene (AA), which comprises reacting ethylene (E) with chlorotrifluoroethylene (CTFE) in the presence of acrylic acid (AA), and comprises reacting ethylene (E) with chlorotrifluoroethylene (CTFE) in the presence of acrylic acid (AA). A method in which the reaction of E) with chlorotrifluoroethylene (CTFE) is carried out in a suspension. The reaction of ethylene (E) with chlorotrifluoroethylene (CTFE) in the presence of acrylic acid (AA) is carried out at a temperature of −40 ° C. to + 100 ° C. and a pressure in the range of 0.5 to 100 bar. The method according to claim 3. -A substrate having at least one surface [Surface (S)] and
-The layer (L1) which is at least one layer [layer (L1)] directly adhered to the surface (S) and contains the polymer (P) according to claim 1 or 2.
Goods including. The article according to claim 5, wherein the base material is a polymer base material or a metal base material. The article according to claim 6, wherein the polymer base material is selected from the group containing a polyamide base material, a polyarylamide base material, and a polyimide base material. Within the group in which the metal substrate comprises stainless steel, zinc-plated stainless steel, carbon steel, copper, aluminum, iron, zinc, cadmium, magnesium, brass, bronze, Monel®, Inconel®. The article of claim 6, which is selected. A method for manufacturing an article as defined in any one of claims 5 to 8.
(I) A step of preparing a base material having at least one surface (S);
(II) A step of producing a layer (L1) which is at least one layer (L1) directly adhered to the surface (S) and contains the polymer (P) defined in claim 1 or 2.
How to include.